DE1229730B - Process for the production of acrylonitrile copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08f

German class: 39 c -25/01

Number: 1229 730

File number: A 46317IV d / 39 c

Filing date: June 15, 1964

Opening day: December 1, 1966

AcryMtril-Polymerisate.with 85% or more polymerized Acrylonitrile are generally made from aqueous monomer solutions. or dispersions produced using redox systems as catalysts. Although this procedure gives satisfactory yields, the polymers produced in this way do not have a sufficient degree of whiteness and insufficient heat discoloration resistance.

Attempts have been made to remedy this disadvantage by adding a water-soluble polymer solution to the polymer solution Salt, namely potassium aluminum sulfate, has been added (see British patent specification - 907 178). The whiteness and the degree of discoloration when exposed to heat could not be improved sufficiently will.

There has now been a process for the production of AcryMtril copolymers with at least 85 percent by weight Acrylonitrile by polymerizing acrylonitrile with one or more polymerizable Vinyl monomers using a redox system in the presence of a water-soluble one Found a salt with which it is then possible to use acrylonitrile copolymers to produce in high yields, which have an improved degree of whiteness and a lower sensitivity to the action of heat if sodium, potassium or magnesium sulfate is used as the water-soluble salt.

The copolymers produced according to the invention are therefore particularly suitable for the production of Fibers and yarns with high whiteness, good heat resistance and good base dyeability.

According to a preferred embodiment of the method of the invention, acrylonitrile is with a Vinyl monomers with side groups with a fairly high space requirement, optionally with another Mixed monomers with acid function, polymerized. Peroxy compounds are used as redox catalysts, such as sodium persulfate or potassium persulfate and reducing agents such as sulfur dioxide, Pyrosulfite, sodium or potassium metabisuMte, in an activator to catalyst ratio between 3: 1 and 1: 1 used and in the presence of sodium sulfate, potassium sulfate or magnesium sulfate in amounts of 1 to 10%, preferably 3 to 7%> polymerized. The ratio of water to monomers is 3: 1 to 7: 1 and is determined by suitable Additions of sodium bicarbonate to a pH value below 7, preferably between 2.5 and 3.5, adjusted.

The vinyl monomers with side groups that take up a lot of space and are copolymerized with acrylonitrile can be: methyl methacrylate, ethyl process for the production of
AcryMtril copolymers

Applicant:

A.C.S.A. - Applicazioni Chimiche S.p. A.,

Milan (Italy)

Representative:

Dr.-Ing. H. Negendank, patent attorney,

Hamburg 36, Neuer Wall 41

Named as inventor:

Corrado Mazzolini,

Sergio Lo Monaco, Mestre-Venice (Italy)

Claimed priority:

Italy of June 18, 1963 (12 646)

methacrylate, butyl methacrylate, octyl methacrylate, methoxethyl methacrylate, Phenyl methacrylate, cyclohexyl methacrylate, dimethylamidoethyl methacrylate and the associated esters of acrylic acid, acrylamides and methacrylamides and their substituted by alkyl groups Products, unsaturated ketones such as methyl vinyl ketone, phenyl vinyl ketone, methyl isopropenyl ketone, Vinyl esters of carboxylic acids, such as vinyl formate, vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl thioacetate, vinyl benzoate, esters of ethylene carboxylic acids, such as Maleic acid, fumaric acid, citraconic acid, mesaconic acid, aconic acid (4,5-dihydro-5-keto-3-furancarboxylic acid), N-alkyl maleimide, N-vinyl carbazole N - vinyl succinic acid imide, N - vinyl phthalimide, vinyl ether, styrene and its alkyl derivatives.

The mixed monomer with an acid function available to fix the basic dyes, which with Acrylonitrile is polymerizable together can be selected from the following group: itaconic acid, Cinnamic acid, maleic acid or maleic anhydride, carboxyvinylphthalic acid, vinylbenzenesulfonic acid, allyloxethylsulfonic acid, Methallyloxäthylsulfonsäure Allylthioäthylsulfonsäure, Isopropenylbenzenesulfonsäure, Vinyl bromobenzenesulfonic acid, vinymuoroben-

609 729/405

3 4

zolsulfonic acid, vinylethylbenzenesulfonic acid, vinyldi- publications of the National Bu-

chlorobenzenesulfonic acid, vinyltrioxybenzenesulfonic acid, reau of Standards in Paper Trade

Acetylethylene sulfonic acid, naphthylethylene sulfonic acid, Journal, 38 [1936] pp. 103 to 108).

Propylene sulfonic acid and its alkali metal or

Ammonium salts, as well as p-methylacrylamide-benzene- 5 3.Thermal sensitivity (heat-sensitive-

sulfonate, sodium, S-methylallyl sodium benzene sulphide): indicated by the change in color.

phonate ether, sodium methallylsulfonic acid or meth-

Sodium acrylamide-benzenesulfonate. 4. Dyeability: Determined by the amount of color

To the advantages of the method according to the invention material (CI. Basic Blue 22) from a solution

To clearly show, examples and io of 7 g / l in a bath of 100 ° C for 2 hours are then used

given a table, of which the table was fixed, the ratio polymer

the degree of whiteness and the heat resistance of about 1:20 to bath. The measurement results

Polymerisate refers. are compiled in the table.

From the table it can be seen that with

same initiator and same viscosity of the poly- 15 example
merisate the presence of Na, K or Mg sulfate

the original color and the heat-sensitive- It was the same polymerization as in the

speed of both the polymers and the fibers, Comparative Experiment A in the presence of 5 parts by weight

improves. Sodium sulfate using 0.6 weight

ao share catalyst and 1.38 parts by weight activator

Comparative experiment A repeated, the ratio of activator to catalyst 2.3: 1.

Two aqueous streams containing 0.6 parts of K ₂ S ₂ O ₈ - Example 2 - are continuously fed into a 3-1 polymerization reactor
Catalyst or 1.38 parts of KHS0 ₃ activator to 25

out, the latter being _{partially neutralized by NaHCO 3} and the ratio of activator to catalyst test A was 2.3 in the presence of 3 weight lysers. Furthermore, a third monomer part of sodium sulfate is repeated using 0.4 Gerenstrom of a mixture of 91.9 parts by weight of catalyst and 0.92 parts by weight of active acrylonitrile and 8.1 parts by weight of vinyl acetate, the ratio of activator being added . . Catalyst was 2.3: 1. '

The total amount of water added is

2.3 l / h and the total amount of monomer 0.5 l / h. B e i s ρ i e 1 3

The reaction temperature is kept at 50 ° C.

The aqueous dispersion of the polymer formed was the same as in the comparison is then removed through an overflow pipe, 'Experiment A was filtered in the presence of 6% magnesium, with water, then with acetone and then sulfate using 0.4 parts by weight of Katamals washed repeatedly with water to remove all foreign analyzer and 0.92 parts by weight of activator, substances and the unconverted monomer to be produced, the ratio of activator to catalyst being 2.3: 1 distant, and then in an oven was 40 for 12 hours.

dried at 80 ° C. Among the standard polymer B ice board 4
About 350 to 400 g of copolymer per hour are obtained in which the acrylic polymerisation as in the comparative experiment A nitrile and the vinyl acetate in a ratio of 93: 7 was polymerised in the presence of 4% sodium sulfate. Note is included. On this copolymer 45 turning of 0.5 parts by weight of catalyst and the following measurements were made: 1.5 parts by weight of activator were repeated, the

The ratio of activator to catalyst was 2.3: 1. ■ 1. Intrinsic viscosity (η) in dimethylformamide (in ml / g).

Example 5
2. Original color of the polymer. For the 50

Numerical evaluation of the color is based on The same polymerization as in the comparison the CIE system for color display and measurement test A was referred to in the presence of 4% magnesium solution. According to this system, sulfate is repeated, using 3.81 water per hour and the color as a function of the predominant wave 0.8351 monomer using 0.6 gel length (LOD), the purity (p) and the catalyst and 55 parts by weight 1.38 parts by weight of active standard lighting Ci emission source corresponds to vator, the ratio of stock in a black body at 6200 ° K) related vator to catalyst being 2.3: 1.
Expressed brightness (B):

Comparative experiment B

β 18 p * ² 96 ^ ⁰

W - '- 5 In a 3-1 polymerization reactor are continuously

^{υ> υ} ° · * natural aqueous solutions of 0.5 parts by weight

where B - brightness, K ₂ S ₂ O (, - catalyst and 1.5 parts by _{weight of SO 2 active}

vator added, the latter partly through

p * = s purity, multiplied by a 65 NaHCO _{3 is} neutralized and the ratio activator

Correction factor -F = / (LOD), is 3: 1 for the catalytic converter. Furthermore, a mono-

(see Journal of the Optical Society merenstrom from a mixture of 90.5 weight

of America, 28, p. 52 [1938], and share acrylonitrile, 96 parts by weight of vinyl acetate and

5 6

0.5 part by weight of cinnamic acid was added. The train run is. There is also a third stream of monomers

speed of the water is 2.3 l / h and the added, which consists of a mixture of 93 weight

those of the monomers 0.5 l / h. share acrylonitrile and 7 parts by weight methyl meth-

The reaction temperature is about 50 ^° C. acrylate. The inflow speed of the water

hold, and the aqueous suspension of the 5 thus obtained is 2.3 l / h and that of the monomer 0.5 l / h.

Polymer is drawn off through an overflow pipe, the reaction temperature is kept ^{at 50 0 C,}

filtered, with water, acetone and then again with The aqueous suspension of the polymer thus obtained

Water washed repeatedly to sates all foreign matter is then drained through an overflow pipe

and remove the unreacted monomer, and filter, with water, acetone and then again with

the whole thing is then washed repeatedly in a suitable oven for 12 hours ο water to remove all foreign matter

the dried at 8O ⁰ C. To remove under the standard and the unreacted monomer,

Polymerization conditions are mixed at about 350 g and finally in an oven for 12 hours

polymer obtained per hour in which the acrylic 8O ⁰ C dried.

nitrile, vinyl acetate and cinnamic acid in the under standard polymerization conditions

ratios 92.5: 1: 0.5 are polymerized. 15 about 350 g of copolymer per hour are obtained, in which, according to our findings, the

_. . . ,, ratio of acrylonitrile to methacrylate is 93: 7.
Examples

The same polymerization 'as in the comparative. .

Experiment B was carried out in the presence of 5% magnesium

sulfate using 0.5 parts by weight of Kata- The same polymerization as in the comparative

lysator and 1.51 parts by weight of activator repeated, experiment D was in the presence of 5% sodium sulfate

the ratio of activator to catalyst being 3: 1 using 0.6 parts by weight of catalyst

fraud. and 1.38 parts by weight of activator repeated, wherein

25 the ratio of activator to catalyst at 2.3: 1

Comparative experiment C was.

A 3-1 polymerization reactor are continuously comparative experiment E
ierlich two aqueous streams of 0.6 parts by weight

K ₂ S ₂ O ₈ catalyst or 1.38 _{parts by weight SO 2} - 30 A 3-1 polymerization reactor are continuously

Activator fed, the latter partly with two aqueous streams of 0.8 parts by weight

_{NaHCO 3 is} neutralized and the ratio of activator K ₂ S ₂ O ₈ catalyst or 0.8 parts by weight of a partially

to catalyst is 2.3: 1. wise SO ₂ activator neutralized with NaHCO ₃

Furthermore, a stream of monomers is fed in from a mi, the ratio of activator to catalyst

Schung of 90.5 parts by weight of acrylonitrile, 9 parts by weight is 1: 1. Furthermore, a third stream is made

share vinyl acetate and 0.5 parts by weight of potassium salt added to monomers, which are made from a mixture of

added to the vinylbenzenesulfonic acid. 90.5 parts by weight of acrylonitrile, 9 parts by weight of vinyl

The amount of water supplied was 2.3 l / h, and the acetate and 0.5 part by weight of the sodium salt of benzene

The amount of monomer fed in was 0.5 l / h. sulfonic acid p-methallyl ether

The reaction temperature was about 50 ⁰ C 40

held and the aqueous suspension of the thus obtained. ^

Polymerisates drawn off through an overflow pipe, then CH ₂ = C - CH ₂ - O - / \ - ■ SO ₃ Na

filtered, with water, acetone and then again with water ^ '

ser washed repeatedly to remove all foreign matter and that
remove unreacted monomers, and finally 45
lent dried in an oven for 12 hours at 80 ° C.

Under standard polymerization conditions were passed. The inflow speed of the water

about 350 g of copolymer obtained per hour, in contributes 2.3 l / h and that of the monomer 0.5 l / h.

which the acrylonitrile, the vinyl acetate and the potassium- The reaction temperature was kept at about 50 ° C-

salt of vinylbenzenesulfonic acid according to our feast 50 th. The aqueous suspension of the resulting poly

position in the proportions 92.5: 7: 0.5 polymerizates was drawn off through an overflow pipe,

were merized. then filtered, with water, acetone and then again

washed with water repeatedly to remove all foreign matter

Example 7 and to remove the unreacted monomer, and

55 finally in an oven at 8O ⁰ C for 12 hours

The polymer described in Comparative Experiment C dried.

sation was made in the presence of 5 ° / ₀ potassium sulfate under these polymerization conditions were

using 0.6 parts by weight of catalyst obtained about 350 g of copolymer per hour, in

and 1.38 parts by weight of activator repeated, the ratio of acrylonitrile to vinyl acetate increasing

the ratio of activator to catalyst was 2.3: 1. 60 p-methallyl ether of sodium benzene sulfonate = 92.5:

7: 0.5.

Comparative experiment D Example 9
Two aqueous streams of 0.6 parts by weight are continuously fed into a 3-1 polymerization reactor. The same polymerization as in the comparative K ₂ S ₈ O ₈ catalyst or 1.38 parts by weight was partially carried out in the presence of 5% sodium sulfate with NaHCO 3 ₃ neutralized SO ₂ activator is supplied, and 0.8 parts by weight of activator are repeated, the ratio of activator to catalyst = 2.3, the ratio of catalyst to activator being 1: 1.

1 V cla UvIl % Salt based on sales Own Base color * 99.1 B. 8th warmth B. Staining the monomers; viscosity ² ) sensitivity ⁴ ) availability "Comparative experiment A % Oi) IP 94.7 IP 15.2 1 68.5 ml / g ^x ) 97.7 94 ³ ) 9.6 10.2 2 5NA ₂ SO ₄ 70 149 98.5 95.2 10.5 10 10.5 3 3Na ₂ SO ₄ 69.2 151 99.1 98.7 96 7.1 7th 10 4th 6MgSO ₄ 75 168 99.4 96.1 8.4 11 9.8 5. 4Na ₂ SO ₄ 70 159 99.7 98.4 94.9 8.5 7.3 10.2 Comparative experiment B 4MgSO ₄ 75 150 99.4 94.4 9.2 26th 11.4 6th • - · 71 129 99.2 94.8 9.1 12.3 16.5 Comparative experiment C 5MgSO ₄ 74 154 98.2 94.8 19.1 16 16.2 7th - 68 162 99 95.6 12.9 10.6 15.6 Comparative experiment D 5K ₂ SO ₄ 79.6 148 98.6 94.5 11.2 21.5 15.4 8th - 71 141 99.2 95.3 9.8 11 9.7 Comparative experiment E 5Na ₂ SO ₄ 74 160 98.8 95.3 13.2 16.6 9.8 9 - 67.8 148 99.1 953 9.5 11.6 14.9 Comparative experiment 5Na ₂ SO ₄ 81.1 154 98.8 12.2 15.4 (British Batentschrift 138 99.1 10.5 : 907178). 95.3 11.7 According to British patent 5KAl (SO ₄ )., -.71. - : document 907 178 supplement 147 11.5 . game 2, but with 95.8 7.9 Like comparative experiment A, 5MgSO ₄ 74 - but with 143 94.9 6.8 9.8 Like comparative experiment A, 3KAl (SO ₄ ) Sa 72 - but with 151 93.7 10.2 12.0 4KAl (SO ₄ ) U 73 - 148 10.7

) Original color; ² ) Original brightness; ³ ) 'change of base color; ⁴ ) Change in brightness.

Claims (2)

Claims: 35 1. Process for the production of mixed acrylonitrile polymers with at least 85 weight percent acrylonitrile by polymerizing acrylonitrile with one or more polymerizable vinyl monomers using a redox system in the presence of a water-soluble salt, characterized in that as water-soluble salt sodium, potassium or magnesium sulfate is used. 2. The method according to claim 1, characterized in that the amount of salt used in the Range between 0.1 and 10 percent by weight, based on the amount of monomers. Considered publications:
British Patent No. 907 178. 609 729/405 11.66 © Bundesdruckerei Berlin